Reactions of Manganese and Rhenium Vinylidene Complexes with Hydrophosphoryl Compounds

Utegenov, Kamil I.; Krivykh, V. V.; Mazhuga, Andrei M.; Чудин, Олег С.; Smol’yakov, Aleksander F.; Dolgushin, Fedor M.; Goryunov, E. I.; Ustynyuk, Nikolai A.

doi:10.1021/acs.organomet.6b00626

Cited by 8 publications

(3 citation statements)

References 87 publications

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“…Rhodium catalysts were also used to hydrophosphinylate alkynes under microwave irradiation and yielded mono- or double addition products, depending on the loading of the phosphine oxide . Manganese and rhenium catalysts have also been used to effect the single or double hydrophosphinylation of terminal aryl acetylenes, although both required high temperatures …”

Section: Introductionmentioning

confidence: 99%

“…13 Manganese and rhenium catalysts have also been used to effect the single or double hydrophosphinylation of terminal aryl acetylenes, although both required high temperatures. 14 Overall, the hydrophosphination and hydrophosphinylation of acetylenes are both known reactions that have been achieved using a variety of catalysts. In the reported systems, these addition reactions have thus far only been studied independently and have not been examined simultaneously utilizing the same catalytic system.…”

Section: ■ Introductionmentioning

confidence: 99%

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Regioselective Single and Double Hydrophosphination and Hydrophosphinylation of Unactivated Alkynes

2019

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A lanthanum-based N,N-dimethylbenzylamine complex was used as a precatalyst for both hydrophosphination and hydrophosphinylation of alkynes under mild conditions. In the case of hydrophosphination, the catalyst induced monoaddition with high regiospecificity, yielding only the anti-Markovnikov product, and stereoselectivity that could be controlled on the basis of the reaction conditions. Undertaking the catalysis with excess phosphine yielded the E isomer as the major product; however, using excess alkyne, the Z isomer was instead isolated as the major product. A brief investigation into the catalytic cycle suggested that a dimeric form of the lanthanum phosphide active catalyst provided the Z isomers as kinetic products that then underwent isomerization to yield the final E isomers. In the case of hydrophosphinylation, the chemoselectivity depended on the nature of the alkyne used. Terminal alkynes gave only double addition products while both single and double addition products were successfully isolated in the case of internal alkynes. The hydrophosphinylation also showed high chemo- and regioselectivity as only the anti-Markovnikov products were isolated. Monohydrophosphinylation of internal alkynes gave almost exclusively the E isomer, and double hydrophosphinylation of all alkynes led to 1,2-addition products.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Regioselective Single and Double Hydrophosphination and Hydrophosphinylation of Unactivated Alkynes

2019

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“…We performed a computational study with the aid of density functional theory (DFT) methods to investigate the Pd-catalyzed hydrophosphorylation of terminal alkynes with P(O)–H compounds . We found that the hydrophosphorylation proceeds via switchable mechanisms that are influenced by the acidity of substrates and co-catalysts.…”

Section: Introductionmentioning

confidence: 99%

Computational Study Revealing the Mechanistic Origin of Distinct Performances of P(O)–H/OH Compounds in Palladium-Catalyzed Hydrophosphorylation of Terminal Alkynes: Switchable Mechanisms and Potential Side Reactions

et al. 2022

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Pd-catalyzed hydrophosphorylation of alkynes with P(O)−H compounds provided atom-economical and oxidant-free access to alkenylphosphoryl compounds. Nevertheless, the applicable P(O)−H substrates were limited to those without a hydroxyl group except H 2 P(O)OH. It is also puzzling that Ph 2 P(O)OH could co-catalyze the reaction to improve Markovnikov selectivity. Herein, a computational study was conducted to elucidate the mechanistic origin of the phenomena described above. It was found that switchable mechanisms influenced by the acidity of substrates and co-catalysts operate in hydrophosphorylation. In addition, potential side reactions caused by the protonation of Pd II −alkenyl intermediates with P(O)−OH species were revealed. The regeneration of an active Pd(0) catalyst from the resulting Pd(II) complexes is remarkably slower than the hydrophosphonylation, while the downstream reactions, if possible, would lead to phosphorus 2pyrone. Further analysis indicated that the side reactions could be suppressed by utilizing bulky substrates or ligands or by decreasing the concentration of P(O)−OH species. The presented switchable mechanisms and side reactions shed light on the cotransformations of P(O)−H and P−OH compounds in the Pd-catalyzed hydrophosphorylation of alkynes, clarify the origin of the distinct performances of P(O)−H/OH compounds, and provide theoretical clues for expanding the applicable substrate scope of hydrophosphorylation and synthesizing cyclic alkenylphosphoryl compounds.

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Chemo-, regio-, and stereoselective catalyst-free addition of diphenylphosphine oxide to acetylenic amino ketones. Synthesis of Z-diphenylphosphoryl(organylamino)alkenones

Verkhoturova,

Volkov,

Bidusenko

et al. 2024

Russ Chem Bull

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Reactions of Manganese and Rhenium Vinylidene Complexes with Hydrophosphoryl Compounds

Cited by 8 publications

References 87 publications

Regioselective Single and Double Hydrophosphination and Hydrophosphinylation of Unactivated Alkynes

Regioselective Single and Double Hydrophosphination and Hydrophosphinylation of Unactivated Alkynes

Computational Study Revealing the Mechanistic Origin of Distinct Performances of P(O)–H/OH Compounds in Palladium-Catalyzed Hydrophosphorylation of Terminal Alkynes: Switchable Mechanisms and Potential Side Reactions

Chemo-, regio-, and stereoselective catalyst-free addition of diphenylphosphine oxide to acetylenic amino ketones. Synthesis of Z-diphenylphosphoryl(organylamino)alkenones

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